Hair waving lotion of alkali metal and ammonium salts of an aliphatic mercaptan carboxylic acid



United States HAIR WAVIN G LOTION F ALKALI METAL AND AMMONIUM SALTS OFAN ALIPHATIC MER- CAPIAN CARBOXYLIC ACID Harry Martin, Monroe, N. Y.,assignor, by mesne assignments, to Permanent Hair Waving Corporation,Norfolk, Va., a corporation of Virginia No Drawing. Original applicationApril 4, 1942, Serial No. 437,628. Divided and this application March15, 1952, Serial No. 276,883

20 Claims. (Cl. 132-7) This invention relates to compositions suitablefor hair curling, and is herein disclosed in some detail as embodied incompositions suitable for cold hair waving. This application is adivision of my application Serial No. 437,628, filed April 4, 1942, nowabandoned, which latter is in part a continuation of my priorapplication Serial N0. 383,204, filed March 13, 1941, now Patent No.2,350,178 of May 30, 1944.

It has been found possible in the past, it dangers and unpleasantnesswere ignored, to efiect the cold waving of hair with inorganic sulfidesor hydrosulfides, but some people seem to have been fatally poisoned bysolutions of those inorganic materials, and, moreover, the odor of thesubstances used was highly ofiensive and nauseous.

It has been hitherto proposed to use the hydrochloride of thesulfur-bearing amino acid cysteine, but that is commercially prohibitiveand was used at pH of about 11, which irritated the operatorshands andthe scalp carrying the treated hair.

Other substances have been tried, but had to be so strongly alkalinewhen used that they stung the hands of the operator or the scalp of theperson whose hair was being curled, and for that reason, werepractically worthless for most purposes.

According to the present invention, the foregoing and other difiicultiesare overcome, and a curling solution is provided which ishighlyeffective in the cold, is harrn less, is economical to prepare, issafe in unskilled hands, is so nearly odorless that its odor is easilycovered up, leaves notoxic or otherwise objectionable residue, does notinjure the hands of an operator or the scalp of a person whose hair isbeing curled, and does not act as a depilatory;' Moreover, the solutionis in every way suitable to put into the hands of the average housewife.Modified solutions may be used hot, if weaker, or may be useful whenspeed is desired.

In one form of the invention, ten grams of sodium thioglycolate weredissolved in 100 cc. of water, making a'solution of pH 6 to 7, andapplied to the hair wound on a rod at room temperature. In the course ofan hour to three hours, the still wound hair was washed with warm water,say below 125 F. The hair appeared unharmed and waved permanently to thewound shape.

depending on the texture and condition of the hair, or,

for bleached or dyed hair, ten minutes, and wet with a solution made bymixing 500 cc. of 20 volume hydrogen peroxide with 500 cc. water and 30grams tartaric acid. This neutralizes the alkalinity of theammonia-containing solution and, incidentally raises the hair to 125 F.

Evaporation of the water from the chemicals used Patented Mar. 10, 195910 grams thiglycolic acid 7 grams sodium hydroxide 20 cc. 26 B. aquaammonia 100 cc. water or witch-hazel 2 drops synthetic oil (to give apositive odor) of pine.

This formula was effective on fine hair (which yields slowly totreatment), as well as on bleached dyed and coarse hair, the timevarying from five to thirty minutes, when cold.

For domestic use by unskilled persons modified formulas were the best,using 4% to 10% of a soluble thioglycolate and a pH between 7 and 9.5.Above pH 10, a depilatory action shows itself in partial or incipientdestruction of the hair fibre. Occasionally a 3% solution is advisable,and as high as 15% is usable by a skilled operator under someconditions.

It is usually most satisfactory to make the solution alkaline by aquaammonia, but alkali metal salts give a tighter curl on some types ofhair. Many common salts, even sodium chloride, sodium sulphate, andammonium acetate, when present, exert definitely deleterious effects.

Often the best effects are obtained by adding an organic base to replacepart of the sodium as:

10 grams thioglycolic acid 3 grams monoethanol amine 1 gram sodiumthioglycolate were dissolved in less than 100 cc. water, 26 B. aquaammonia wa sadded to make pH 8.5 and water added to make 100 cc.

Another material was made with 6.5 grams thioglycolic acid cc. waterMonoethanolamine to make pH 7 Aqua ammonia to make pH 9.05 Water to makecc.

Solutions with a pH of 9.02, which is obviously about 9, have proved themost satisfactory compromise solution for all around use, consideringfineness of hair, temperature, time and other considerations of beautyparlor practice. One such solution was 7 grams thioglycolic acid 100 cc.water Sodium or potassium hydroxide solution 8.5 grams thiolactic acid90 cc. water Monoethanolamine added to make pH 8 Then 26 B. aqua ammoniato make pH 8.5 diluted to 100 cc.

Where a curling solution was found to be used promptly so that nodeterioration occurred by standing, the best results were obtained byusing appropriate solutions of thiocarbarnate salts. These thiocarbamatesalts were easily made by mixing for example, two moles ofmonocthanolamine with one mole of carbon disulphide.

The reaction was instantaneous so that the carbon disulphide should beusually added slowly to avoid spattering.

The resulting dithiocarbamate in suitable solution, curled hair rapidlyand safely and was easily washed out, to fix the curl. As little as a 4%solution was found useful especially in the cold. The product may becalled a solution of monoethanolammonium-N-oxyethyldithiocarbamate. Itwas stable over a period of some weeks.

When isopropanolamine was substituted for the monoethanolamine, ityielded a parallel product of about equal utility. That product may becalled isopropanolammonium dithiocarbamate. It was possible to useammonium dithiocarbamate made in the same way, by using an excess ofammonium hydroxide, although its odor made it less useful.

Other useful results were obtained by producing amides and treating hairwiththem in solution, thus avoiding any uncertainty or difficultyarising from the possible instability of the thiocarbamate.

N-oxyethylthioglycolamide was made by dehydrating a mixture ofmonoethanolamine and thioglycolic acid. The mixture was heated at about140 C. at a pressure of 15 to 22 mm. until the proper computed amount ofwater was removed and collected. The resulting product was ready forimmediate use, when in proper solution.

lsopropanolamine substituted for the monoethanolamine under the sameconditions, yielded a corresponding product similarly useful. Theproduct was N-oxypropyldithioglycolamide.

When butanolamine was substituted for the monoethanolarnine under thesame conditions, it yielded a corresponding product similarly useful.

Monothioglycolates of glycols or other polyhydroxyl alcohols were alsofound useful in hair curling, but not equal to the amides. These weremade as follows:

To thioglycolic acid, containing about a fraction of 1% of sulphuricacid, was added slowly with intermittent cooling, a slight excess ofethylene oxide yielding a viscous liquid, ready to use in hair curlingwhen in suitable solution after removal of the sulphuric acid as bybarium carbonate. The product in solution wasethyleneglycolmonothioglycolate.

Propylene oxide substituted for the ethylene oxide yielded thecorresponding propyleneglycol product which was about equally useful inhair curling. Glycidol when substituted for the ethylene oxide yieldedthe corresponding glyccryl monothioglycolate, which also proved usein]in hair curling.

Monothioglycerine and thiosalicylic acid were found to be usable insuitable concentrations though inferior to most of the other materialsnamed above.

It was found that many of these materials were effective on the otheranimal fibres and were useful in treating woolen textiles, for example,to make them crease resistant and make them hold creases, as forinstance in men's trousers.

A pink flannel made by Botany Worsted Mills E. B. was wet with a 4%solution of monoethanolammonium-N-oxyethyldithiocarbamate with aquaammonia added to make a pH of about 9, and heated with a crease for 5 toseconds to 200 F. on a flat surface with an electric iron, washed withvery dilute acetic acid and then with very dilute hydrogen peroxide.

The material was hung up and dried. It dried with the crease ironed inat one line, but dried flat elsewhere where treated and the crease waspermanent. The untreated area wrinkled. The color was slightly affected,but this may be allowed for in dyeing. The feel of the treated portionwas improved to that of a much more expensive flannel. I

A purple soft fine womans wear wool with a tendency to crepe when wettedmade by the same company was similarly treated with the same solution,at a temperature of about 180 F. with a crease. The color was slightlyaltered, which could be allowed for in the dyeing. The material retainedits crease where treated and dried fiat where treated, but becamecrepe-like elsewhere.

A blue mans worsted cloth, like a summer alpaca made by the same peoplewas similarly treated at F. The crease was permanent and the treatedarea re.- mained flat.

It will be noted that most of the named compounds contain both ahydroxyl and a mercapto group and com tain an organic radical either inthe acid or the basic element. 7

Having thus described my invention and illustrated its use, what I claimas new and desire to secure by Letters Patent is:

1. A hair waving lotion consisting essentially of an aqueous solution ofat least 4% thioglycolic acid, by weight of the solution, the solutionhaving been neutralized to a pH of about 8 with an alkali metalhydroxide to attain the equivalence point for the resultingthioglycolate salt, and having then been brought to a pH in the range ofabout pH 9 to about pH 10 by the addition of ammonia.

2. A hair waving lotion consisting essentially of an aqueous solution ofat least 4% thioglycolic acid, by weight of the solution, sufiicientalkali metal alkali to produce a pH of about 8 with this thioglycolicacid concentration, and sufiicient ammonia to give an ultimate pH in therange of about pH 9 to about pH 10.

3. A hair waving lotion consisting essentially of an aqueous solution ofthioglycolate, equivalent: to 1 to 15% thioglycolic acid by weight ofthe solution, sufiicient alkali metal alkali to produce a pH of about 8with this thioglycolic acid concentration, and sufficient ammonia togive an ultimate pH in the range of about pH 9 to about pH 10.

4. A hair waving lotion consisting essentially of an aqueous solution ofat least 4% thioglycolic acid, by weight of the solution, sufficientalkali metal alkali to produce a pH of at least 6 with this thioglycolicacid concentration, and sufficient ammonia to give an ultimate pH ofabout 7 to about 9.5.

5. A hair waving lotion consisting essentially of an aqueous solution ofl to 15% thioglycolic acid by weight of the solution, sufiicient alkalimetal alkali to produce a pH of at least 6 with this thioglycolic acidconcentration, and sulficient ammonia to give an ultimatepH of about 7to about 9.5.

6. A hair waving lotion consisting essentially of an aqueous solution of4 to 10% thioglycolic acid by weight of solution, sufiicient alkalimetal alkali to produce a pH of about 8 with this thioglycolic acid,concentration, and sufiicient ammonia to give an ultimate pH in therange of about 9 to about 10.

7. A hair Waving lotion consisting essentially of, an aqueous solutionof 4 to 10% thioglycolic acid by weight of solution, sufiicient alkalimetal alkali to produce a pH of at least 6 with this thioglycolic acidconcentration, and suflicient ammonia to give an ultimate pH of about 7to about 9.5.

8. A hair waving lotion consisting essentially of an aqueous solution ofalkali metal and ammonium salts of an aliphatic mercaptan carboxylicacid of not more than three carbon atoms, equivalent to from 1 to 15%aliphatic mercaptan carboxylic acid by weight of solution, having a pHin the range of about pH 9 to about pH 10, the proportion of said alkalimetal salt being such that it would produce a pH of at least 6 with thisconcentration of said acid in the absence of ammonia.

9. The product of claim 8 wherein at least a part of the alkali metal issubstituted by a lower alkanolamine.

10. The method of permanently changing the configuration of hair on theliving human scalp including the steps of treating the hair with thepermanent waving solution of claim 8 and then fixing said configuration.

11. The method of permanently changing the configuration of hair on theliving human scalp including the steps of treating the hair with thepermanent waving solution of claim 9 and then fixing said configuration.

12. A hair waving lotion consisting essentially of an aqueous solutionof alkali metal thioglycolate and ammonium thioglycolate, equivalent toat least 4% thioglycolic acid by weight of solution, having a pH in therange of about pH 9 to about pH 10, the alkali metal proportion ofalkali metal thioglycolate being such that it would produce a pH ofabout 8 with this thioglycolic acid concentration in the absence ofammonia.

13. The method of permanently changing the configuration of hair on theliving human scalp including the steps of treating the hair with thepermanent waving solution of claim 12 and then fixing saidconfiguration.

14. A hair waving lotion consisting essentially of an aqueous soultionof an alkali metal thioglycolate and ammonium thioglycolate, equivalentto from 1 to 15% thioglycolic acid by weight of solution, having a pH inthe range of about pH 9 to about pH 10, the proportion of alkali metalthioglycolate being such that it would produce a pH of at least 6 withthis thioglycolic acid concentration in the absence of ammonia.

15. The method of permanently changing the configuration of hair on theliving human scalp including the 6 steps of treating the hair with thepermanent waving solution of claim 14 and then fixing saidconfiguration.

16. A hair waving lotion consisting essentially of an aqueous solutionof an alkali metal thioglycolate and ammonium thioglycolate, equivalentto from 3 to 15% thioglycolic acid by weight of solution, having a pH ofabout 7 to about 9.5, the proportion of alkali metal thioglycol'atebeing such that it would produce a pH of at least 6 with thisthioglycolic acid concentration in the absence of ammonia.

17. A hair waving lotion consisting essentially of an aqueous solutionof sodium thioglycolate and ammonium thioglycolate, equivalent to from 4to 10% thioglycolic acid by weight of solution, having a pH of about 7to about 10, the proportion of sodium thioglycolate being such that itwould produce a pH of at least 6 with this thioglycolic acidconcentration in the absence of ammonia.

18. A hair waving lotion comprising about 10 grams of thioglycolic acid,about 7 grams of sodium hydroxide, about 20 cc. of aqua ammonia of about26 B. dissolved in about 100 cc. of water.

19. The method of permanently changing the configuration of hair on theliving human scalp including the steps of treating the hair with thepermanent waving solution of claim 18, the hair being physicallycontoured to the desired configuration, and then fixing saidconfiguration.

20. The method of permanently changing the configuration of hair on theliving human scalp including the steps of treating the hair with thepermanent waving solution of claim 18, the hair being physicallycontoured to the desired configuration, varying the time of treatmentfrom five to thirty minutes, according tothe type of hair treated, andthen fixing said configuration.

References Cited in the file of this patent UNITED STATES PATENTSSpeakman May 21, 1940 Evans June 27, 1944 OTHER REFERENCES

1. A HAIR WAVING LOTION CONSISTING ESSENTIALLY OF AN AQUEOUS SOLUTION OF AT LEAST 4% THIOGLYCOLIC ACID BY WEIGHT OF THE SOLUTION, THE SOLUTION HAVING BEEN NEUTRALIZED TO A PH OF ABOUT 8 WITH AN ALKALI METAL HYDROXIDE TO ATTAIN THE EQUIVALENCE POINT FOR THE RESULTING THIOGLYCOLATE SALT, AND HAVING THEN BEEN BROUGHT TO A PH IN THE RANGE OF ABOUT PH 9 TO ABOUT PH 10 BY THE ADDITION OF AMMONIA
 18. A HAIR WAVING LOTION COMPRISING ABOUT 10 GRAMS OF THIOGLYCOLIC ACID. ABOUT 7 GRAMS OF SODIUM HYDROXIDE, ABOUT 20 CC. OF AMMONIA OF ABOUT 26* BE DISSOLVED IN ABOUT 100 CC. OF WATER 